Organic polymeric compositions containing nitrilo methylol-phosphorus polymers and bromine compounds



United States Patent ORGANIC POLYMERIC COMPOSITIONS CONTAIN- ING NITRILOMETHYLOL-PHOSPHORUS POLY- MERS AND BROMINE COMPOUNDS Wilson A. Reeves,Carl Hamalainen, and John D. Guthrie, New Orleans, La., assignors to theUnited States of America as represented by the Secretary of AgricultureNo Drawing. Application November 9, 1954, Serial No. 467,899

6 Claims. (Cl. 117-136] (Granted under Title 35, U. S. Code (1952), sec.266) A non-exclusive, irrevocable, royalty-free license in the inventionherein described, for all governmental purposes, throughout the world,with the power to grant sublicenses for such purposes, is hereby grantedto the Government of the United States of America.

This invention relates to reducing the flammability of organic textiles.More particularly, the invention provides textile treating compositionsadapted to incorporate the elements phosphorus, nitrogen, and bromineinto organic textiles in a manner and amount in which the elements coactto materially reduce the flammability of the textile.

Prior work has resulted in the development of a variety of polymerscapable of being produced by condensation and/or esterification reactioninvolving tetrakis(hydroxymethyl)phosphonium chloride, which has theformula (HOCH2)4PC1, and is abbreviated THPC, and/or tris-(hydroxymethyl)phosphine oxide, which has the formula (HOCH2)3PO, and isabbreviated THPO. The methylolphosphorus, PCH2OH groups, of each ofthese compounds are capable of either: (1) condensing with a compoundwhich is capable of condensing with formaldehyde; or, (2) beingesterified by an esterifying agent which is capable of esterifyingmethanol. Compounds of the group, THPC, THPO, and derivatives of eitherof them which contain a plurality of methylol-phosphorus groups of theparent compounds, are hereinafter referred to by the term phosphoruscompounds.

The polymers capable of being produced by condensation and/oresterification reactions of the phosphorus compounds can be produced inthe form of cross-linked polymers or thermosetting resins; and,hereinafter, these polymers are referred to by the termmethylol-phosphorus polymers or resins. The compounds capable of eithercondensing with formaldehyde or esterifying methanol are hereinafterreferred to by the term methylolreactive compounds."

The methylol-phosphorus polymers are characterized by recurringstructural units containing phosphorus atoms in radicals of the group(CH2)4PC1 and (-CH2)3PO. Methylol-phosphorus alkyds are produced byreacting at least one of the phosphorus. compounds with at least onepolycarboxylic acid esterifying agent. Phenolic methylol-phosphoruspolymers are produced by reacting at least one of the phosphoruscompounds with at least one phenolic compound.

Certain nitrogen containing methylol-phosphorus polymers, which arehereinafter referred to as nitrild methylol-phosphorus polymers orresins, are particularly useful as textile flammability retardants.These resins are adapted to being partly or completely formed within thetextile by impregnating the textile with an aqueous solution ordispersion of their resin forming reactants, and causing the reactantsto react in situ until an insolubilized resin is produced. The nitrilomethylol-phosphorus polymers are capable of being produced by condensingat least one of the phosphorus compounds, with the climina tion ofwater, with at least one organic nitrogen compound having a molecularweight of not more than about 800 and containing at least one trivalentnitrogen atom and at least two members of the group H and Cit ZOIIattached to trivalent nitrogen atoms. This class of organic nitrogencompounds is hereinafter referred to by the term "nitrogen compounds."Methods of producing the nitrilo methylol-phosphorus polymers andemploying them to reduce the flammability of textiles are morecompletely described in copending patent applications, Serial No.378,437 filed September 3, 1953; Serial No. 393,021 now Patent2,772,188, and Serial No. 393,023 now Patent 2,795,569 filed November18, 1953. The nitrilo methylol-phosplrorus polymers are cross-linkedphosphorus and nitrogen containing polymers in which the recurringstructural units each contain a phosphorus atom that is a component of aradical of the group (CI-Iz)4PCl and (CH2)3PO and is linked to at leasttwo trivalent nitrogen atoms by connecting structures of the group CH2and -CR2OCR2 where R is a member of the group hydrogen and alkylradicals.

While the nitrilo methylol-phosphorus polymers are particularly goodtextile flammability reducing agents, the production of such an agentwhich imparts the maximum reduction in textile flammability per part ofresinous impregnant is one of the goals being sought in the field ofimparting flame resistance to textile materials.

A primary object of the present invention is to provide improved nitrilomethylol-phosphorus textile flammability reducing compositions in whichthe desirable properties characteristic of the nitrilo methylol-phosphorus compositions (properties such as causing only a slight reductionin hand, feel, tear strength, and the like desirable textile properties)are retained and augmented by the incorporation of certain brominecontaining materials.

Heretofore, the efficiency of the nitrilo methylol-phosphorus polymers(the amount of flame resistance imparted per unit weight of resin)seemed to be substantially completely dependent upon the amount andratio of nitrogen and phosphorus contained in the polymers. The presenceor absence of halogen seemed to exert little, if any, effect upon theefficiency. For example, a nitrilo methylol-phosphorus polymer producedunder conditions yielding a polymer containing from about 1 to 12%chlorine exhibits substantially the same efficiency as one containingthe same amount and ratio of nitrogen and phosphorus, produced underconditions yielding a substantially halogen free polymer, Whereas onecontaining an appreciably different amount or ratio of nitrogen andphosphorus exhibits an appreciably different efficiency.

We have now discovered that when nitrilo methylolphosphorus polymershaving a nitrogen and phosphorus content within certain ranges of bothamount and nitrogen-to-phosphorus ratios are mixed with a certainproportion of non-volatile compositions containing firmly attachedbromine, the resulting compositions exhibit a flame reducing efficiencywhich is materially greater than that of compositions which differ onlyin the absence of the bromine containing compositions.

In general, in accordance with the present invention, a homogeneouspolymeric mixture is formed by mixing at least one nitrilomethylol-phosphorus polymer and at least one organic material containingat least 10% of bromine in the form of bromine atoms attached to carbonatoms in proportions selected so that phosphorus contained in structuresof the group (CH2)4PC1 and (CH2)3P0 amounts to at least 3% of the totalweight of the mixture and from about 0.5 to 15 parts of nitrogencontained in nitrilo groups and from 0.5 to 15 parts of bromine in theform of bromine atoms attached to carbon atoms are present per part ofsaid phosphorus.

Throughout the specification and claims, the term parts and percent areused only to refer to parts or percent by weight.

The nitrilo methylol-phosphorus polymers can be formed in the polymericmixture, for example, by mixing the bromine containing compound withresin forming reactants of the nitrilo methylol-phosphorus polymer andconverting the reactants to a polymer in situ.

The bromine containing polymeric mixtures provided by this invention canbe produced in the form of liquid or solid compositions. They arehomogeneous mixtures characterized by a particularly high resistance toburning and the property of imparting high degree of resist ance toburning to other materials. These mixtures are generally useful wherevermixtures predominating in cross-linked polymers are useful. Illustrativeexamples include their use in the production of molded synthetic plasticarticles such as buttons, containers, electrical insulators and thelike; synthetic coatings such as paints, varnishes, and the like;adhesives; and impregnating agents for textiles, ropes, paper and thelike.

These bromine containing polymeric mixtures are particularly suited foruse in the impregnation of organic textiles to reduce theirflammability. These mixtures can be used in the treatment of vegetabletextile materials such as cotton, fiax, linen, ramie, and the like,chemically modified vegetable textile materials such as cyanoethylated,carboxymethylated, aminoethylated cottons and the like; regeneratedcellulosic textiles such as the viscose rayons; or proteinaceoustextiles such as silk, wool, and the like. The textile materials can betreated in the form of slivers, yarns, threads, or fabrics. The polymerscontained in the mixtures can be separately formed or can be produced insitu in the textile by a reaction of materials with which the textile isimpregnated. The mixtures can be used as the only material with whichthe textile is impregnated or used in conjunction with other textilefinmeproofing, creaseproofing, wrinkleproofing and the like textiletreating agents; or in conjunction with textile lubricants, waterrepellents, and the like textile treating agents.

The bromine containing compositions which can be mixed with the nitrilomethylol-phosphorus polymers to provide the polymeric mixtures of thepresent invention comprise non-volatile compositions which areunreactive toward cellulosic materials, nitrilo methylol-phosphoruspolymers, and nitrilo methylol-phosphorus resin forming reactants, andare compositions containing at least about 10% of bromine in the form ofbromine atoms attached to carbon atoms.

One preferred class of such bromine containing compositions comprisesthe polybromo alcohol neutral esters of phosphonitrilic halides.Illustrative examples of such esters include the 2,3-dibromopropylesters of the phosphonitrilic chlorides, and the like esters, disclosedin U. S. Patent No. 2,681,295.

Another preferred class of such bromine containing compositions comprisethose of the polymeric addition products of (a) Ci-zpolyhalohydrocarbons containing at least two atoms of the group bromineand chlorine attached to the same carbon atom and (b) terminallyunsaturated alkenol esters of phosphorus nitrilic halides which areaddition products containing at least about 10% bromine. Such additionproducts are capable of being produced by a free radical initiatedreaction between the components of a mixture of reactants consisting ofat least one of the groups, (a) a polymerizable terminally unsaturatedalkenol ester of a phosphonitrilic halide and (b) a polybromohydrocarbonof the group in which X represents bromine and Y represents bromine,chlorine, or hydrogen; in which mixture the reactants and the proportionin which they are mixed are selected so that the mixture contains atleast about 10% of bromine in the form of bromine atoms attached tocarbon atoms; with said reaction being conducted until the resultingpolymeric addition product contains at least about 10% bromine. Suitableprocesses of producing typical members of such polymeric additionproducts are described in more detail in copending application SerialNo. 467,900, filed of even date. Terminally unsaturated alkenol estersof phosphorus nitrilie halides which are particularly useful inproducing such polymeric addition prod ucts include the allyl esters ofthe triand tetrameric phosphonitrilic chlorides, bromides, and the like.Terminally unsaturated Ca-s alkenol esters of the lower polymericphosphonitrilic chlorides are particularly preferred.Polybromohydrocarbons which are particularly useful in producing suchpolymeric addition products include bromoform, carbon tetrabromide, andthe like. Polybromomethancs are preferred polybromohydrocarbons.

Another preferred class of bromine containing materials, comprises thoseof the analogous polymeric addition products of terminally unsaturatedN-alkenylated melamines which contain at least about 10% bromine in theform of bromine atoms attached to carbon atoms and which are free ofmethylol reacting groups. Such polymeric addition products are capableof being produced by a free radical initiated addition reaction betweenthe components of a mixture of reactants consisting of at least onemember of each of the first two groups, (a) a polymerizable terminallyunsaturated alkenylated melamine of the formula in which R represents alower alkyl radical or a terminally unsaturated alkenyl radical, and atleast two of the latter radicals are present in each compound, (b) apolybromo hydrocarbon of the class bined weight of (a) and (b) of alower aliphatic aldchyde; in which mixture the reactants and theproportion in which they are mixed are selected so that the mixturecontains at least about 10% of bromine in the form of 7 bromine atomsattached to carbon atoms; with said reacucts include N,N-diallylmelamine, N,N-diallyl methylolmelamine, N,N-tetra-allylmelamine and thelike. The terminally unsaturated N-alkenylated melamines containing fromabout 2 to 6 Ca-s alkenyl radicals are preferred, the allylic melaminesbeing particularly preferred. Poly- 7 bromo hydrocarbons which can beused in producing such polymeric addition products include bromoform,carbon tetrabromide, and the like. The polybrnmomethanes are preferredpolybromohydrocarbons.

Another preferred class of bromine containing compositions comprises thepolymeric addition products of polybromo hydrocarbons and polymerizablealiphatic acrylamides which addition products contain at least about 10%of bromine in the form of bromine atoms attached to carbon atoms. Suchaddition products are capable of being produced by a free radicalinitiated addition reaction between the components of a mixture ofreactants consisting of at least one member of each of the first twogroups, (a) polymerizable compounds of the formula o OH:N(R) ti! CH=CH1(b) a polybromohydrocarbon of the class also i i as defined above and(c) from to 20% of the combined weight of (a) and (b) of a loweraliphatic aldehyde; in which mixture the reactants and the proportion inwhich they are mixed are selected so that the mixture contains at leastabout of bromine in the form of bromine atoms attached to carbon atoms;with said reaction being conducted until the resulting polymericaddition product contains at least about 10% bromine. Aliphaticacrylamides which can be used in the production of such polymericaddition products include N,N'-methylcnebis-acrylamide, and the like.Acrylamide and methylenebis-acrylamides are particularly preferred.Polybromohydrocarbons which can be used in the production of suchpolymeric addition products include bromoform, carbon tetrabromide, andthe like. The polybromomethanes are preferred polybromohydrocarbons.

Suitable processes of producing typical members of the addition productsof both the N-alkenylated melamines and the aliphatic acrylamides withpolybromohydrocarbons are described in greater detail in copendingapplication Serial No. 467,898, filed of even date.

Another preferred class of bromine containing materials comprises thepolymeric addition products of polybromohydrocarbons and polymerizabletrialkenyl phosphates which addition products contain at least about 10%of bromine in the form of bromine atoms attached to carbon atoms. Suchpolymeric addition products are capable of being produced by a freeradical initiated addition reaction between the components of a mixtureof reactants consisting of at least one member of each of the groups,(a) polymerizable alkenyl phosphates of the formula OR Ito-i=0 in whichR represents an alkyl radical or a terminally unsaturated alkenylradical and R represents a terminally unsaturated alkenyl radical, and(b) a polybromohydrocarbon of the class 6 and it i as defined above; inwhich mixture the reactants and the proportions in which they are mixedare selected so that the mixture contains at least about 10% of brominein the form of bromine atoms attached to carbon atoms, with saidreaction being conducted until the resulting polymeric addition productcontains at least about 10% bromine. Trialkenyl phosphates which can beused in the production of polymeric addition products include triallylphosphate, trimethallyl phosphate, and the like. Terminally unsaturatedC trialkenyl phosphates are preferred, the allylic phosphates are beingparticularly preferred. Polybromohydrocarbons which can be used in theproduction of such polymeric addition products include bromoform, carbontetrabromidc, dibromodichloromethane and the like. The polybromomethanesare particularly preferred. Suitable processes of producing typicalmembers of such polymeric addition products are described in greaterdetail in copending application Serial No. 403,943, now Patent 2,778,747filed January 13, 1954, and U. S. Patents Nos. 2,686,768 and 2,686,769.

Other suitable bromine containing materials include these brominatedpolymers of triallyl phosphate and the like bromine containing polymersof unsaturated phosphates described in U. S. Patent Nos. 2,660,524 and2,660,543, and the like materials which contain at least about 10% ofbromine in the form of bromine atoms attached to carbon atoms.

Preferred nitrilo methylol-phosphorus polymers comprise those producedby reacting reactants of the group, phosphorus compounds andpolyfunctional nitrogen compounds, selected so that phosphorus containedin phosphorus compounds amounts to at least about 0.5% of the totalweight of the reaction mixture and so that from about 1.0 to 2.0 partsof nitrogen contained in nitrogen groups are present per 1 part ofphosphorus contained in phosphorus compounds.

A portion of the bromine contained in the polymeric mixtures provided bythe present invention can be contained in the nitrilomethylol-phosphorus polymer. Bromine containing nitrilomethylol-phosphorus polymers can be produced by reacting reactants ofthe group phosphorus compounds, polyfunctional nitrogen compounds, andpolyfunctional methylol reacting compounds. A process of producing suchbromine containing nitrilo methylolphosphorus polymers is described ingreater detail in copending application Serial No. 467,898 filed of evendate.

While the phosphonium salt phosphorus compounds used in the productionof the nitrilo methylol polymerforming reactants or polymers employed inthe present invention are usually in the form of the phosphoniumchloride, they can be replaced by the analogous phosphate or the likephosphonium salt; and the phosphonium salt derivatives of THPC can bereplaced by the analogous phosphonium salts of acids other thanhydrochloric acid.

Where the polymeric mixtures provided by this invention are employed astextile flammability reducing agents, the textile can be impregnatedwith the bromine containing composition and then reimpregnated with thenitrilo methylol-phosphorus polymer or vice versa, or the brominecontaining composition and the nitrilo methylolphosphorus polymer can beincorporated into an organic or aqueous liquid, in the form of asolution, dispersion. emulsion, or suspension, and simultaneouslyapplied to the textile by impregnating the textile with said liquid. Thelatter method comprises a preferred method of applying; the polymermixtures to textiles.

In general, whether the nitrilo methylol-phosphorus polymer and thebromine containing material are mixed before or after application to atextile, it is preferable to apply the nitrilo methylol-phosphoruspolymer to the textile in the form of either a further polymerizablepoly mer or a mixture of nitrilo methylol-phosphorus resin formingreactants and insolubilizing the nitrilo methylolphosphorus polymer insitu in the textile. Textiles impreguatcd with a liquid containing thenitrilo methylolphosphorus resin forming materials are preferably driedby heating them to form about 60 to 125 C. for from about 2 to 15minutes, with the lower temperature being used with the longer time, toevaporate volatile materials. The insolubilization of the nitrilomethylol-phosphorus resin forming materials can be accomplishedthermally by heating the textiles containing them to a temperature offrom about 125 to l70 C. for from about 2 to 15 minutes, with the lowertemperature being used with the longer time. Alternatively, theinsolubilization can be accomplished by reacting the resin formingmaterials in situ in the textile with ammonia, preferably by the processdescribed in copcnding application Serial No. 393,021 filed November 18,i953, now Patent No. 2,772,188.

The application of the polymeric mixtures provided by this invention totextiles can be accomplished by means of the usual procedures andapparatus for impregnating textiles with resinous materials. Thesemixtures can further be mixed with the usual textile softening,lustering. lubricating and the like textile treating agents.

The phosphorus compounds which can be used in the production of nitrilomethylol-phosphorus polymers for use in this invention comprise at leastone member of the group Tl-IPC. THPO. and compounds derived from eitherof them which contain a plurality of the methylolphosphorus groups ofthe parent compounds. These derivative phosphorus compounds are theproducts obtained by partially reacting THPC. THPO, or a mixturethereof, with either a monoor polyfunctionnl methylolreactive compounduntil some but not all of the methylolphosphorus groups of THPC or TH?!)react. Such compounds can be monomers in which the methylolphosphorusgroups are attached to a single phosphorus atom or further polymerizablcpolymers in which some of the methylol-phosphorus groups are attached todifferent phosphorus atoms of the polymer molecules.

illustrative examples of suitable polyfunctiona] methylol-rcnctivecompounds which are capable of condensing with formaldehyde include:polyamines such as ethylenedinmine, tctramethylenepentamine, and thelike; alicyclic amines such as cyclohexylaminc, cyclopentamine,mothylolated cyclohexylamines. and the like; aromatic amines such asaniline, phenyldiamine, and the like; imincs such as cthylenimine, andthe homologs of the polymers of ethylenimine. and the like; compoundssuch as melam ne or gtiauidine; amido compounds. such as urea, alkylatedhomologs and analogs thereof, acrylamide, cyanamide. and the like; aminoacids such glycine, lysine. arginine, and the like; and the bromineanalogs of any such organic nitrilo compounds. These compounds caneither be employed as the polyfunctional nitrogen compound or as areactant for partial reaction with THPC or THPO to produce a nitrilogroup containing derivative phosphorus compound.

(ill

Other suitable nitrilo group containing derivative phosphorus compoundscan be produced by a similar partial reaction of THPC, THPO, or amixture thereof with the analogous organic nitrilo compounds whichcontain only one member of the group H or CHzOH attached to a trivalentnitrogen atom. Illustrative examples of such monofunctional nitrilocompounds (monofunctional in they contain a single methylol reactivefunctional group) include: open chain polyamines such asN,l"l,N-trimethyl ethylenediamine; alicyclic amines such as N butylcyclohexyl amine; aliphatic amines such. as diethanolamine; amides suchas N-allyl acrylamide; amino acids such as N-methyl glysine; and thebromo analogs of any such nitrilo compounds that contain at least onebrom ne atom attached to a carbon atom that is attached to anothercarbon atom.

Illustrative examples of polyfunctional methylol reactive compoundswhich are capable of condensing with formaldehyde also include: phenols,naphthols, and haloand/or hydrocarbon-substituted phenols and naphtholr;such as phenol, vinylphenol, resorcinol, catcchol, hydroquinone,phloroglucinol, para-tertiary-amylphenol, allyl phenol,ortho-hromophenol, bromo-hydroouinonc 2,4-dibromo-l-naphthol, and thelike.

Any of the above phenolic compounds can be partially reacted with THPC,THPO, or a mixture thereof to produce a monomeric or polymeric compoundwhich is an aromatic group-containing derivative phosphorus compoundcontaining at least two methylol-phosphorus groups and which is suitablefor employment in the production of nitrilo methylol-phosphoruspolymers.

Illustrative examples of polyfunctional methylol reactive compoundswhich are capable of estcrifying methyl alcohol include: saturatedaliphatic polycarboxylic acids. such as oxalic, malonic, methylsuccinic,malic, tartaric, citric and like acids; unsaturated aliphaticpolycarboxylic acids, such as maleic, itaconic, aconitic and like acalicyclic polycarboxylic acids, such as pinic, homopinic, thehexahydrophthalic and like acids; aromatic polycarboxylic acids, such asthe phthalic, the benzenetricarboxylic, diphenic, chlorendic, and likeacids; polycarboxylic acid anhydrides, such as succinic, maleic,phthalic. chlorendic, and the like acid anhydrides; and polycar boxylicacid halides, such as oxalyl, succinyl, the phthalyl. and the like acidhalides.

Any of the above polycarboxylic acid estcrifying agents or theirmonocarboxylic acid analogs can be partially reacted with THPC, THPO ormixtures thereof to produce monomeric or polymeric derivative phosphoruscompounds, containing ester groups and at least two methylok phosphorusgroups, which are suitable for employment in the production of nitrilomethylol-phosphorus polymers.

Free radical reaction initiators which can be used in the abovedescribed free radical initiated reactions be tween variouspolybromohydrocarbon and various unsaturated compounds includesubstantially any compounds which are susceptible to being decomposed toyield free radicals under the influence of heat, light, or fast ch.mental particles formed in the course of the reaction. Illustrativeexamples of such free radical reaction initiators include peroxides suchas dibenzoyl peroxide, ditertiary-butyl peroxide, hydrogen peroxide,alkali metal persulfatcs, benzoyl hydropcroxide, cumene hydroperoxide,and the like; azo compounds such as 2,2'-bisazoisobutyronitrile; andketones in conjunction with actinic light and the like reactioninitiators. The peroxides, and. where the reaction is conducted in anaqueous emulsion reaction medium, the Water soluble peroxides, arepartic ularly preferred.

The following examples are illustrative of certain details of thepresent invention.

In the examples, the flame resistance of various resin impregnatedcloths were compared by the strip flame test method. In this method astrip of the cloth, which is about half an inch wide and about 3 incheslong, is

supported at one end so that the strip extends toward some degreebetween and 180 relative to a vertical azimuth. The unsupported ends ofthe cloth strips are ignited by contacting them with a flame until thecloth 10 An aqueous solution was made containing 15.7% THPC, 10% ResloomHP, 10% urea and 3% triethanolamine.

A mixture of 2 parts of the PNE-CHBl'a emulsion and begins to burn. Assoon as the cloth is ignited the flame 5 1 part of the THPC solution wasused to pad 8 oz. twill used to ignite it is removed. The flammabilityof the to approximately 66% wet pickup. The twill was dried cloths iscompared on the basis that, when so supported 10 minutes at 100 C. thencured 6 minutes at 140 C. and ignited, the cloths have a much greatertendency to After the fabric was washed and dried it had a resin burnwhen they are supported so that they extend straight add-on of 12.9 Thetreated fabric passed the 135 down and are ignited at the bottom.Untreated cellulosic l0 angle in the strip flame test and almost passedthe 180 cloth will fail at 0 degrees (i. e. will burn when supportedangle in the strip flame test. to extend straight up and ignited at thetop). A very Example, i resistant 5 1 V1 g 13 3 9: 2 Samples of 8.5 oz.sateen were treated with (l) the 315E023? 3M2 2132s.;f iamfiisiim 5311fwill 15 PNHHBIH addm of Exam THPC not fa exce t at some an, 18 g about90 and 180 mutation (an aqueous solution containing 17.7% THPC. P d d d(H h th 11% Resloom HP and 8.8% urea), and (3 the THPC l supporte to exen Qwnwar y so t at a resin in combination with PNE-CHBla adduct. Afterflame 1s propagated at least somewhat upwardly) padding they were dried10 minutes at 100 C., cured 6 Example 1 20 min. at 140 C. then washedand dried. The following A piece of 80 sq. print cloth was moistenedwith 10% table the data solution of 2,3-dibromopropyl diester of PNClsin acesample wet Final tone, then washed in hot water 10 minutes anddried 15 s a- Treating solution p p. es n Matc minutes in the oven at110 C. The cloth had a gain in mm percent $5 2 test weight of 8.2%. Itpassed the 90 angle in the strip flame test. A portion of this samplewas further treated I (A) PNE OHBnadductm 76 151 Failedwith an aqueoussolution containing 12% THPC, 7.7% C 67 Resloom HP and 5.7% urea to anadditional resin pickup 70 Passedof 13.5% giving a total resin add-on of21.7%. It passed 68 1M the 180 angle in the strip flame test.

Another piece of 80 sq. print cloth was first treated with an aqueoussolution containing 12% THPC, 7.7% Resloom HP and 5.7% urea to a finaladd-on of 13.5% resin. This sample passed the 120 angle in the stripflame test. A portion of this sample was further treated with a 10%acetone solution of the 2,3-dibrornopropyl diester of PNClz to anadditional gain in weight of 6.9%. This Was a total gain in weight of20.4%. It passed the 180 angle in the strip flame test.

A sample of fabric treated with THPC resin alone to a THPC resin contentof 21.6%, only passed the 135 to 140 angle in the strip flame test.

(Above data show synergistic eflect of the combined treatment.)

Example 5 Samples of 8.5 oz. sateen and 8.0 oz. twill were treated withthe PNE-CHBrs adduct of Example 3. Other samples of the fabrics weretreated with a mixture containing 25 parts adduct emulsion and 75 partsTHPC resin-forming solution (an aqueous solution containing 15.7% THPC,10% Resloom HP, 10% urea and 3% tricthanolamine). The fabrics weredried, cured and washed as in Examples 3 and 4. The following tablelists data on the treated fabrics:

Example 2 Sample Nature Wet Final Match Samples of 80 sq. print clothwere treated with two desk of Treating mum-0n pickup, pickup, mtconcentrations of 2,3-drbromopropyl drester of PNCla to minim Samplepercent pe give add-on of 9.5% and 5.8% respectively. These were furthertreated with an aqueous solution containing 12% A E W) 66 13.0 ailed.THPC, 7.7% Resloom HP and 5.7% urea. Also, a sam- 13 Sateen" m- 1m 156Adduct. ple of sq. print cloth treated initially with an aqueous C TwmMixture gmsflnn 63 13,8 1mm solution containing 12% THPC, 7.7% ResloomHP and D sateen Mixture 251 71 15. D0, 5.7% urea was further treatedwith an acetone solution S 1 D b It d bl t 1 l d n if n amp 6 El 0V9 W35qul e [HE G O 3111M cr'tng, 111 ll ('1' d l) 1 El?- of the dlester' 55accelerated launderings the treated fabric passed the match test de- Thefollowing table lists the data for these samples:

scribed in Example 4).

Strip Tear Strength Sample designation Treatment I Treatment II flametest strength, retention, P, Bromine,

(angle), lbs. percent percent percent degrees 00 4. 6 115 45 4. 6 1122.8 70 0. 93 0.0 dicster 13.3% THPC resin 180 3.1 77 1. 53 5.00 diester13.3% THPC resin 180 3.4 85 1.27 3.70 3% THPC resin. 57 dicster 180 3.075 1.37 3.04 3% THPC resin 10 n diester 180 3.3 83 1. B5 6.94 6% THPCresin. 1.6 1. 74 0.0

(The above data show the synergistic efl'cct of the combination.)

Example 3 Example 6 An emulsion containing 31% solids was prepared byreacting 1 part of an allyl neutral ester of a phosphonitrilic chloride(PNE) with 0.6 part bromofortn (CHBrs).

A THPC resin formulation containing 38 parts THPC, 24 parts Resloom HP,24 parts urea, 3 parts triethanol- 75 amine and parts water wasprepared. A sample of 8 oz. twill was padded with the above resinsolution, dried 6 minutes at 100 C., cured 6 minutes at 140 C. thenwashed and dried. The final resin add-on was 16.4%. The sample passedthe 135 angle in the strip flame test.

A mixture of 75 parts of the above THPC resin formulation and 25 partsof a triallyl phosphate bromoforrn adduct containing 1:0.6 molar ratioof TAP to CHBrs and approximately 40% solids content was prepared. Asample of twill was padded with this mixture. dried 6 minutes at 100 C.,cured 6 minutes at 140 C. then washed and dried. The final resin add-onwas 13.8% and this sample also passed the 135 angle in the strip fiametest and appeared to be slightly better than the sample treated withTHPC resin alone. However, the sample treated with the combinationtreatment had 2. less resin add-on than the sample treated with the THPCresin alone.

Example 7 Ten grams of 2.3 dibromopropyl neutral ester of PNClg weredissolved in 10 grams chloroform and then emulsified with l grams of 2%aqueous polyvinyl alcohol solution. The emulsion was mixed with a THPCresin forming solution containing 19 grams THPC, 12 grams Rcsloom HP, 12grams urea, 3 grams triethanolamine and 75 grams of water. A piece of 8oz. twill and a piece of 8.5 oz. sateen were padded with the abovemixture. dried 6 minutes at 100 C., cured 6 minutes at 140 C., andfinally washed and dried. The following table summarizes the results:

A control THPC resin treated 8 oz. twill of 16.4% resin add-on passedthe 135 angle in the strip flame test.

We claim:

of pliosphonitrilic chloride, an addition product of a tc minnllyunsaturated alkenol ester of phosphonitrilic rh oride and a polybromo ClZ hydrocarbon containing at int two bromine atoms attached to the samecarbon atom. as addition product of an N-allrenylated melamine a dpolybromo C1a hydrocarbon containing at least o bromine atoms attachedto the same carbon atom, an a iition product of an aliphatic acrylamideand a n i omo C14 hydrocarbon containing at least two bromin: at msattached to the same carbon atom, and an 1 him product of a trialkenylphosphate and a polybromo Ci z hydrocarbon containing at least twobromine moms attached to the same carbon atom, the phosphorus ll saidnitrilo mcthyiol-phosphorus polymer being LTYI". .Ened in structures ofthe group consisting of C-Cl-lzhiCl and (-CH2)3PO in amounts to at least0.5% of the total weight of the mixture, and from about I to 20 parts ofnitrogen contained in nitrilo groups and from about 0.5 to 20 parts ofbromine contained in the form of bromine atoms attached to carbon atomsbeing present per 1 part of phosphorus contained in said structure.

2. An organic textile treating agent comprising an aqueous liquidcontaining a mixture of at least one nitrilo rnethylol-phosphoruspolymer and a compound containing at least 10% of bromine in the form ofbromine atoms attached to carbon atoms, said compound being selectedfrom the group consisting of a polybromoaleohol ester oi phosphonitrilicchloride, an addition product of a terminally unsaturated alkenol esterof phosphonitrilic chlo ride and a polybromo C1- hydrocarbon containingat least two bromine atoms attached to the same carbon atom, an additionproduct of an N-alkenylated melamine and a polybromo C1-z hydrocarboncontaining at least two bromine atoms attached to the same carbon atom,an addition product of an aliphatic acrylarnide and a polybrorno C1-2hydrocarbon containing at least two bromine atoms attached to the samecarbon atom, and an addition product of a trialkenyl phosphate and apolybromo C1-2 hydrocarbon containing at least two bromine atomsattached to the same carbon atom, the phos phorus in said nitrilomcthylol-phosphorus polymer being contained in structures of the groupconsisting of (CH2)4PC1 and (-CH2)3PO in amounts to at least 0.5% of thetotal weight of the mixture, and from about 0.5 to 20 parts of brominecontained in the form of bromine atoms attached to carbon atoms beingpresent per 1 part of phosphorus contained in said structure.

in a process of reducing the flammability of an or ganic textile byimpregnating the textile with a. nitrilo methylol-phosphorus polymerproduced by reacting at least one compound of the group consisting of(HOCH MPCI, (HOCH2)3PO and the derivatives of either of them containinga plurality of residual PCHzOH groups of the parent compound with atleast one organic nitrogen compound having a molecular weight of lessthan about 400 and containing at least one trivalent nitrogen atom andat least two members of the group consisting of H and CHzOH attached totrivalent nitrogen atoms, the improvement which comprises mixing withthe nitrilo methylol-phosphorus polymer impregnant a compound containingat least about 10% of bromine in the form of bromine atoms attached tocarbon atoms, said compound being selected from the group consisting ofa polybromoalcohol ester of phosphonitrilic chloride, an additionprodnot of a terminally unsaturated alkenol ester of phosphonitrilicchloride and a polybromo C1-2 hydrocarbon containing at least twobromine atoms attached to the same carbon atom, an addition product ofan Nalkenylated melamine and a polybromo C1 z hydrocarbon containing atleast two bromine atoms attached to the same carbon atom, an additionproduct of an aliphatic acrylamide and a polybromo Ci z hydrocarboncontaining at least two bromine atoms attached to the same carbon atom,and an addition product of a trialkenyl phosphate and a polybromo C1-2hydrocarbon containing at least two bromine atoms attached to the samecarbon atom, to provide in the textile a mixed impregnant in whichphosphorus in said nitrilo mcthylol-ohosphorus polymer is contained instructures of the group consisting of (CH2)4PC] and (---CH2)3PO inamounts to at least 0.5% of the total weight of the mixture, and inwhich from about 1 to 20 parts of nitrogen contained in nitrilo groupsand from about 0.5 to 20 parts of bromine contained in the form ofbromine atoms attached to carbon atoms are present per 1 part ofphosphorus contained in said structure.

4. The process of claim 3 in which the bromine con taining compound isan addition product of a neutral allyl ester of a phosphonitrilicchloride and bromoform.

5. The process of claim 3 in which the bromine containing compound is anaddition product of triallyl phosphate and bromoform.

6. The process of claim 3 in which the bromine containing compound is a2,3-dibromopropanoi neutral ester of a phosphonitrilic chloride.

(References on following page) 2,814,578 13 14 References Cited in thefile of this patent 2,668,096 Reeves et a1. Feb. 2, 1954 UNITED STATESPATENTS 2,681,295 Hamalamen June 15, 1954 HER R 2,574,515 Walter et a].Nov. 13, 1951 0T F EN'CES 2,5 0,543 Walter et 1 24, 5 LltflfllFlameprwfing TeXtlle Fabms (P g 947)- (Copy in Division 25.)

3. IN A PROCESS OF REDUCING THE FLAMMABILITY OF AN ORGANIC TEXTILE BYIMPREGNATING THE TEXTILE WITH A NITRILO METHYLOL-PHOSPHORUS POLYMERPRODUCED BY REACTION AT LEAST ONE COMPOUND OF THE GROUP CONSISTING OF(HOCH2)4PCI, (HOCH2)3PO AND THE DERIVATIVES OF EITHER OF THEM CONTAININGA PLURALITY OF RESIDUAL PCH2OH GROUPS OF THE PARENT COMPOUND WITH ATLEAST ONE ORGANIC NITROGEN COMPOUND HAVING A MOLECULAR WEIGHT OF LESSTHAN ABOUT 400 AND CONTAINING AT LEST ONE TRIVALENT NITROGEN ATOM AND ATLEAST TWO MEMBERS OF THE GROUP CONSISTING OF H AND CH2OH ATTACHED TOTRIVALENT NITROGEN ATOMS, THE IMPROVEMENT WHICH COMPRISES MIXING WITHTHE NITRILO METHYLOL-PHOSPHORUS POLYMER IMPREGNANT A COMPOUND CONTAININGAT LEAST ABOUT 10% OF BROMINE IN THE FORM OF BROMINE ATOMS ATTACHED TOCARBON ATOMS, SAID COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OFA POLYBROMOALCOHOL ESTER OF PHOSPHONITRILIC CHLORIDE, AN ADDITIONPRODUCT OF A TERMINALLY UNSATURATED ALKENOL ESTER OF A PHOSPHONITRILICCHLORIDE AND POLYBROMO C1-2 HYDROCARBON CONTAINING AT LEST TWO BROMINEATOMS ATTACHED TO THE SAME CARBON ATOM, AN ADDITION PRODUCT OF ANN-ALKENYLATED MELAMINE AND A POLYBROMO C1-2 HYDROCARBON CONTAINING ATLEAST TWO BROMINE ATOMS ATTACHED TO THE SAME CARBON ATOM, AN ADDITIONPRODUCT OF AB ALIPHATIC ACRYLAMIDE AND A POLYBROMO C1-2 HYDROCARBONCONTAINING AT LEAST TWO BROMINE ATOMS ATTACHED TO THE SAME CARBON ATOM,AND AN ADDITIONAL PRODUCT OF A TRIALKENYL PHOSPHATE AND A POLYBROMO C1-2HYDROCARBON CONTAINING AT LEAST TWO BROMINE ATOMS ATTACHED TO THE SAMECARBON ATOM, TO PROVIDE IN THE TEXITILE A MIXTED IMPREGNANT IN WHICHPHOSPHORUS IN SAID NITRILO METHYLOL-PHOSPHORUS POLYMER IS CONTAINED INSTRUCTURES OF THE GROUP CONSISTING OF (-CH2)4PCI AND (-CH2)3PO INAMOUNTS TO AT LEAST 0.5% OF THE TOTAL WEIGHT OF THE MIXTURE, AND INWHICH FROM ABOUT 1 TO 20 PARTS OF NITROGEN CONTAINED IN NITRILO GROUPSAND FROM ABOUT 0.5 TO 20 PARTS OF BROMINE CONTAINED IN THE FORM OFBROMINE ATOMS ATTACHED TO CARBON ATOMS ARE PRESENT PER 1 PART OFPHOSPHORUS CONTAINED IN SAID STRUCTURE.